Decorative laminated material and decorative molded product using the same

Abstract

The present invention provides a decorative laminate that can be suitably used in insert molding, which maintains surface protection and high adhesion, and facilitates separation of the molded product and the decorative laminate due to the detachability of the adhesive layer when discarded after use. [Solution] The present invention relates to a decorative laminated member having a heat-resistant film layer, an adhesive layer, a design layer, and a resin substrate layer in this order, In a holding strength test of the aforementioned decorative laminated member at 80°C, the displacement after 24 hours when a load of 1 kg was applied was 10 mm or less. The peel strength of the decorative laminated member is 20 N / 15 mm or less. When the decorative laminated member is immersed in the release liquid, the adhesive layer exhibits detachability. We provide laminated components for decorative purposes.

Description

Technical Field

[0001] The present invention relates to a decorative laminated member and a decorative molded product using the same.

Background Art

[0002] Conventionally, a decorative sheet is heated and preformed so as to fit into an injection mold as desired, pre-shaped, installed in an injection mold so that molten resin is injected onto the backing layer side, and then injection molding is performed to weld the molten resin to the backing layer, thereby integrating the decorative sheet and the molten resin. After curing, there is an insert molding method in which the insert molded product is taken out of the injection mold.

[0003] The above-mentioned decorative sheet not only imparts design properties to the molded body, but also imparts a surface protection function. Therefore, a certain degree of high surface hardness is required to prevent damage. On the other hand, when a decorative sheet is bonded to a molded body having a more complex shape, it is necessary to deform and adhere it in a shape along the surface of the molded body. For this reason, the development of a decorative sheet that can achieve both a surface protection function and high adhesion has been desired.

[0004] For example, Japanese Patent Application Laid-Open No. 2013-6346 (Patent Document 1) discloses a decorative sheet with a top coat layer on one side of the decorative sheet, wherein the top coat layer has a surface hardness of at least pencil hardness B at -40 to 130°C and an elongation rate of at least 150% in a tensile test at 150°C. However, such a decorative sheet does not consider recyclability at the time of disposal after use, and it has not been possible to separate the design layer and the injection molding resin having different components in recycling.

[0005] On the other hand, in order to improve the recyclability of the laminated film at the time of disposal after use, an adhesive layer using an adhesive layer having desorbability in a desorbing liquid has been developed.

[0006] For example, Japanese Patent Publication No. 2020-196808 (Patent Document 2) discloses a laminate adhesive containing a polyol and a polyisocyanate that is detachable from composite films. However, such adhesives were not designed for use in insert molding, and there was a possibility that the adhesive would deform due to the high temperature and heat in insert molding. [Prior art documents] [Patent Documents]

[0007] [Patent Document 1] Japanese Patent Publication No. 2013-6346 [Patent Document 2] Japanese Patent Publication No. 2020-196808 [Overview of the project] [Problems that the invention aims to solve]

[0008] The present invention aims to provide a decorative laminate that can be suitably used in insert molding, which maintains surface protection and high adhesion, and which facilitates separation of the molded product and the decorative laminate due to the detachability of the adhesive layer when discarded after use. [Means for solving the problem]

[0009] In other words, the present invention provides the following aspects: [1] A decorative laminate having a heat-resistant film layer, an adhesive layer, a design layer, and a resin substrate layer in this order, In a holding strength test of the aforementioned decorative laminated member at 80°C, the displacement after 24 hours when a load of 1 kg was applied was 10 mm or less. The peel strength of the decorative laminated member is 20 N / 15 mm or less. When the decorative laminated member is immersed in the release liquid, the adhesive layer exhibits detachability. Laminated material for decorative purposes. [2] The decorative laminated member described in [1] further comprises a clear coating layer following a resin substrate layer. [3] The heat-resistant film layer has a thickness of 200 to 500 μm, as described in [1] or [2] for decorative laminated member. [4] The heat-resistant film layer comprises at least one of polypropylene resin, acrylonitrile-butadiene-styrene (ABS) resin, polycarbonate (PC) resin, polymethyl methacrylate (PMMA) resin, and PC-ABS resin [1] or [2], a decorative laminate member. [5] The aforementioned resin substrate layer consists of at least one of polymethyl methacrylate (PMMA), polycarbonate (PC), and PMMA / PC. A decorative laminate member according to [1] or [2] having a thickness of 50 to 300 μm. [6] The aforementioned design layer contains a binder component which is an acrylic resin, and a pigment component which is at least one of a luminous pigment and a coloring pigment. A decorative laminate member according to [1] or [2], wherein the pigment component is contained in 0.5 to 60 parts by mass in solid content in 100 parts by mass of the total solid content of the binder component and the pigment component. [7] The clear coating layer is formed from a radiation-curable clear coating layer forming composition or a thermosetting urethane resin composition [2], a decorative laminate member. [8] A decorative molded product obtained by pressing and integrating a decorative laminated member described in [1] or [2] onto the surface of a resin molded body. [9] The resin molded article is a decorative molded article according to [8], wherein the resin molded article uses the same resin as the heat-resistant film layer.

[10] A method for recycling a decorated molded product, comprising immersing the decorated molded product described in [8] or [9] in a desoldering solution to recover the heat-resistant film layer and the molded body. [Effects of the Invention]

[0010] In the case of a decorative laminated member, considering the recycling of the obtained decorated molded product, the peelability of the adhesive layer is required. On the other hand, if the peelability of the adhesive layer is increased, the adhesive layer cannot withstand the high temperature and high pressure applied by the injection resin during injection molding, so that the shape cannot be maintained, and the design and adhesion cannot be maintained. Therefore, the amount of displacement and peel strength after 24 hours when a load of 1 kg is applied in the holding force test of the decorative laminated member at 80 ° C are important.

Brief Description of Drawings

[0011] [Figure 1] It is a figure which shows typically the layer structure of the decorative laminated member of this invention. [Figure 2] It is a figure which shows typically the measurement of the amount of displacement of this invention. [Figure 3] It is a figure which shows typically the peel strength measurement method of this invention.

Embodiments for Carrying Out the Invention

[0012] The decorative laminated member of the present invention has a cross section as shown in FIG. 1, and has a structure of a heat-resistant film layer, an adhesive layer, a design layer, and a resin base material layer from the bottom of FIG. 1. A clear layer may be provided on the resin base material layer. Although not shown in FIG. 1, the resin base material layer side (the clear layer side when there is a clear layer) contacts the mold. As shown in FIG. 1, the resin of the resin molded body is molded and adhered to the heat-resistant film layer side by a method such as injection molding.

[0013] In the present invention, when a load of 1 kg is applied to the decorative laminated member in the holding force test at 80 ° C, the amount of displacement after 24 hours is 10 mm or less, the peel strength of the decorative laminated member is 20 N / 15 mm or less, and when the decorative laminated member is immersed in the release liquid, the adhesive layer has peelability. By satisfying these requirements, it is possible to satisfy both the shape retention of the decorative laminated member during injection molding (the performance of withstanding the high temperature and high pressure brought by the injection resin) and the peelability during recycling.

[0014] The retention strength test measures the cohesive strength of the adhesive layer by measuring the amount of displacement when a force is applied in a direction 90° to the thickness direction of the decorative laminated member. The displacement should be 10 mm or less, preferably 5 mm or less, and more preferably 2 mm or less. The lower limit of the displacement is 0 mm. A displacement of 10 mm or less significantly suppresses deformation of the adhesive layer during injection molding. On the other hand, if the displacement exceeds 10 mm, deformation of the adhesive layer during injection molding becomes apparent, resulting in poor appearance and poor adhesion.

[0015] The amount of displacement is measured by the following method: A decorative laminated member, cut to a width of 25 mm and a length of 125 mm, is cut with a cutter at a position 25 mm from one end in the longitudinal direction, so as to reach the heat-resistant film layer from the surface on the resin substrate layer side. A hole is made at the other end of the decorative laminated member, a rod-shaped metal is passed through the hole, and the decorative laminated member is suspended vertically from the ground. Then, a load of 1 kg is applied to the surface on the resin substrate layer side with the cut, and the member is left in an 80°C constant temperature bath for 24 hours, and the amount of displacement at the cut portion before and after the 24-hour period is measured.

[0016] In this invention, the decorative laminate member has a peel strength of 20 N / 15 mm or less, preferably 15 N / 15 mm or less, and more preferably 10 N / 15 mm or less. If the peel strength is too low, it may peel off during use, so it is preferable that it be 1 N / 15 mm or more. A peel strength of 20 N / 15 mm or less allows the adhesive layer to exhibit good detachability.

[0017] Here, the peel strength is the 180-degree peel strength (N / 15mm) measured in accordance with JIS Z-0237 "Test Methods for Adhesive Tapes and Adhesive Sheets" under conditions of a temperature of 80°C and a peeling speed of 300 mm / min. Details of the measurement method for peel strength will be described in the example below.

[0018] The decorative laminated member of the present invention requires that the adhesive layer be detachable when immersed in a desoldering solution. Desoldering is a property that contributes to separating the design layer, which is difficult to recycle, from the decorative laminated member during recycling. Good recyclability can be obtained by the adhesive layer detaching when immersed in a desoldering solution, as determined by a desoldering test. This property is related to the composition of the adhesive layer, which will be described later.

[0019] The delamination test involves cutting a decorative laminated material to a predetermined size (specifically, 0.2 cm x 1.5 cm), immersing it in 50 g of a 2% aqueous sodium hydroxide (NaOH) solution at 70°C for 72 hours, stirring, washing with water, drying, and then visually observing and determining the delamination properties of the adhesive layer from the decorative laminated material. In this invention, if the adhesive detaches within 72 hours, it is considered to have good delamination properties.

[0020] The following describes each layer that makes up the decorative laminated member.

[0021] (Heat-resistant film layer) The heat-resistant film layer described above is intended to improve adhesion with the molded article. The heat-resistant film layer is selected according to the resin being molded, but generally, polyolefin resins such as acrylonitrile-butadiene-styrene (ABS) resin and polypropylene resin, styrene resin, acrylic resin, vinyl chloride resin, polycarbonate (PC) resin, and PC-ABS resin are preferred. In particular, it is preferable to include at least one of polypropylene resin, ABS resin, polymethyl methacrylate (PMMA) resin, and PC-ABS resin.

[0022] The thickness of the heat-resistant film layer is preferably 100 to 500 μm, more preferably 200 to 500 μm.

[0023] (Adhesive layer) As mentioned above, the adhesive layer needs to have deleasability when immersed in the deleasability solution. The adhesive layer, for example, contains a polyol and a polyisocyanate, and has an acid value of 8.0 mg KOH / g or higher. Preferably, the polyol contains a polyester polyol component (A), and the polyisocyanate contains an aliphatic polyisocyanate component (B). The combination of the polyester polyol component (A) and the aliphatic polyisocyanate component (B) in the adhesive layer, along with an acid value of 8.0 mg KOH / g or higher, provides excellent deleasability.

[0024] <Polyester polyol component (A)> The polyester polyol component (A) can be selected from conventionally known polyester polyols, and may be used alone or in combination of two or more. The polyester polyol component (A) is not limited to the following, but for example, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, phthalic anhydride, adipic acid, azelaic acid, sebacic acid, succinic acid, glutaric acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, maleic anhydride, itaconic anhydride, and other dibasic acids or their dialkyl esters or mixtures thereof (hereinafter also referred to as carboxyl group components), For example, diols such as ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, butylene glycol, neopentyl glycol, dieopentyl glycol, trimethylolpropane, glycerin, 1,6-hexanediol, 1,4-butanediol, 1,4-cyclohexanedimethanol, 3-methyl-1,5-pentanediol, 3,3′-dimethylolheptane, 1,9-nonanediol, polyoxyethylene glycol, polyoxypropylene glycol, polytetramethylene ether glycol, polyether polyol, polycarbonate polyol, polyolefin polyol, acrylic polyol, polyurethane polyol, or mixtures thereof (hereinafter also referred to as hydroxyl group components), Examples include polyester polyols obtained by reacting [the specified substance] with [the specified substance]; or polyester polyols obtained by ring-opening polymerization of lactones such as polycaprolactone, polyvalerolactone, and poly(β-methyl-γ-valerolactone); and so on. Two or more of the above-mentioned carboxyl group components and hydroxyl group components may be used in combination.

[0025] The above polyester polyol component (A) may be a polyester polyurethane polyol obtained by reacting with diisocyanate, or it may be obtained by further reacting with an acid anhydride. Examples of diisocyanates include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, 1,5-naphthalene diisocyanate, hexamethylene diisocyanate, and hydrogenated diphenylmethane diisocyanate. Examples of acid anhydrides include trimellitic anhydride and trimellitic anhydride esters. Examples of trimellitic anhydride esters include ethylene glycol anhydrotrimellitate.

[0026] As described above, the adhesive layer of the present invention has an acid value of 8.0 mg KOH / g or higher. Therefore, it is preferable that the polyester polyol component (A) has an acid value, and the acid value of the polyester polyol component (A) is preferably 8.0 mg KOH / g or higher, and more preferably 10.0 mg KOH / g or higher. Furthermore, the acid value of the polyester polyol component (A) is preferably 40.0 mg KOH / g or lower. Due to having the above acid value, when the decorative laminated member comes into contact with an alkaline aqueous solution during recycling, the adhesive layer of the present invention is penetrated and decomposed by the alkaline aqueous solution, exhibiting excellent delamination properties.

[0027] When the adhesive layer contains multiple polyester polyol components, the acid value of polyester polyol component (A) can be determined from the acid value of each polyester polyol component and their mass ratio.

[0028] Furthermore, the polyester polyol component (A) preferably contains a polyester polyol with a number average molecular weight (Mn) of 3,000 to 20,000, more preferably 5,000 to 10,000, from the viewpoint of heat sterilization resistance of the adhesive layer and coating properties. A number average molecular weight (Mn) of 3,000 or more of the polyester polyol component (A) is preferable because it allows for coating properties, and a number average molecular weight (Mn) of 20,000 or less is preferable because it improves not only coating properties but also delamination properties.

[0029] The number-average molecular weights specified herein were determined using the Showa Denko GPC (gel permeation chromatography) system "Shodex GPC System-21" with tetrohydrate as the solvent. This value was calculated using Drofuran and converted to standard polystyrene equivalent.

[0030] Furthermore, the adhesive layer of the present invention may contain other polyols besides the polyester polyol component (A) described above. The polyol components that may be included other than the polyester polyol component (A) are not particularly limited, and for example, polycarbonate polyols, polycaprolactone polyols, polyether polyols, polyolefin polyols, acrylic polyols, silicone polyols, castor oil-based polyols, fluorine-based polyols, etc., can be used alone or in combination of two or more types.

[0031] <Aliphatic polyisocyanate component (B)> The aliphatic polyisocyanate component (B) can be selected from conventionally known aliphatic polyisocyanates, and two or more may be used in combination. The aliphatic polyisocyanate (B) is not limited to the following, but compounds derived from well-known aliphatic diisocyanates or alicyclic diisocyanates can be used.

[0032] Examples of aliphatic polyisocyanate components (B) that can be used in the present invention include: Aliphatic diisocyanates such as trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, 1,2-propylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, and 2,6-diisocyanate methyl caproate; Alicyclic diisocyanates such as 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate, 4,4′-methylenebis(cyclohexyl isocyanate), methyl 2,4-cyclohexane diisocyanate, methyl 2,6-cyclohexane diisocyanate, 1,4-bis(isocyanate methyl)cyclohexane, and 1,3-bis(isocyanate methyl)cyclohexane; Alternatively, examples include polyisocyanates such as allophanate-type, nurate-type, biuret-type, adduct-type derivatives, or complexes thereof derived from the above-mentioned aliphatic diisocyanates or alicyclic diisocyanates. Preferably, the derivatives are of the nurate type or the adduct type, and particularly preferably the adduct type. Aliphatic polyisocyanate (B) is preferably a polyisocyanate derived from hexamethylene diisocyanate (hereinafter also referred to as HDI), which allows for easy balancing of laminate properties.

[0033] <Other polyisocyanate components> Furthermore, the adhesive layer of the present invention may contain other polyisocyanates besides the aliphatic polyisocyanate component (B) described above. The polyisocyanate components that may be included other than the aliphatic polyisocyanate component (B) are not particularly limited and include, for example, aromatic aliphatic diisocyanates such as 1,3- or 1,4-xylylene diisocyanate or mixtures thereof, ω,ω′-diisocyanate-1,4-diethylbenzene, 1,3- or 1,4-bis(1-isocyanate-1-methylethyl)benzene or mixtures thereof; Examples include aromatic diisocyanates such as toluene diisocyanate and diphenylmethane diisocyanate.

[0034] The adhesive layer of the present invention may contain other components besides the polyol component and polyisocyanate component described above. These other components may be blended with either the polyol component or the polyisocyanate component, or they may be added when blending the polyol component and the polyisocyanate component.

[0035] The above-mentioned adhesive layer may contain components other than the adhesive resin, curing agent, and components for providing aesthetic properties, as long as they do not impede the purpose of the invention. Examples of such components include ultraviolet absorbers (UVA), light stabilizers (HALS), curing catalysts, antioxidants, surface modifiers, leveling agents, anti-sagging agents, thickeners, defoaming agents, conductive fillers, and solvents.

[0036] Furthermore, solvents may be used to mix the components contained in the adhesive layer and to adjust their viscosity. For example, one or more conventionally known organic solvents used in paints, such as ester-based, ether-based, alcohol-based, amide-based, ketone-based, aliphatic hydrocarbon-based, alicyclic hydrocarbon-based, and aromatic hydrocarbon-based solvents, may be used as the solvent. However, when using the above solvents, if volatile substances remain in the laminated film, they may volatilize, causing pinholes or blistering during decoration of the substrate. Therefore, it is preferable to sufficiently reduce the amount of volatile substances contained in the laminated film.

[0037] (Design layer) The decorative laminated film of the present invention preferably comprises at least one design layer to provide a design feature. Such layers may include a design layer (1) formed by a colored paint composition, a design layer (2) formed by printing, a metallic design layer (3), and the like. The design layer may consist of one of the above-mentioned layers or multiple layers. A unique appearance can be obtained by combining these layers.

[0038] (Design layer (1) formed by a colored paint composition) The colored paint composition that can be used in forming the above-mentioned design layer (1) is not particularly limited, but it is preferable that it contains an acrylic resin and at least one of a glossing agent and a coloring pigment. In addition to the above-mentioned components, the colored paint composition may also contain other components such as ultraviolet absorbers (UVA), light stabilizers (HALS), binder resins and crosslinking agents, pigments, surface modifiers, defoamers, conductive fillers, and solvents. The colored paint composition may be cured by electromagnetic radiation, or it may be thermoplastic or thermosetting.

[0039] (Acrylic resin) The acrylic resin contained in the colored coating composition is not particularly limited, but it is preferably such that its weight-average molecular weight Mw is 10,000 or more and 200,000 or less, and more preferably 30,000 or more and 150,000 or less. If the weight-average molecular weight Mw is less than 10,000, the flexibility of the design layer (C) decreases, and if the weight-average molecular weight Mw exceeds 200,000, it becomes difficult to manufacture the colored coating composition and apply it to the film.

[0040] The above acrylic resin preferably has a Tg of -30°C to 160°C. If the Tg is below -30°C, problems may arise such as a decrease in the tackiness (blocking) of the coating film after coating and drying, and if it exceeds 160°C, molding defects may occur due to increased coating film hardness.

[0041] The binder component used in the design layer may include thermoplastic resins other than acrylic resin, such as cellulose resin, vinyl chloride-vinyl acetate copolymer, polyamide resin, polyester resin, urethane resin, epoxy resin, and styrene resin.

[0042] In this specification, Tg refers to the value measured using a differential scanning calorimeter (DSC) (thermal analyzer SSC5200 (manufactured by Seiko Electronics)) through the following process: Step 1, where the temperature is raised from 20°C to 180°C at a heating rate of 10°C / min; Step 2, where the temperature is cooled from 180°C to -50°C at a cooling rate of 10°C / min; and Step 3, where the temperature is raised from -50°C to 180°C at a heating rate of 10°C / min. Tg is the value obtained from the chart during the heating phase of Step 3. Specifically, Tg is defined as the temperature indicated by the arrow in the chart shown in Figure 2.

[0043] (shining material) The above-mentioned luminous material is not particularly limited, but is preferably at least one selected from the group consisting of aluminum, glass, inorganic pigments, and organic pigments. More specifically, examples include metallic pigments using metallic luminous materials such as coated aluminum, aluminum flakes, copper, zinc, nickel, tin, aluminum oxide, and other metals or alloys; and mica pigments such as interference mica and white mica.

[0044] (Coloring pigments) Examples of coloring pigments include azo lake pigments, phthalocyanine pigments, indigo pigments, perylene pigments, quinophthalone pigments, dioxazine pigments, quinacridone pigments, isoindolinone pigments, and metal complex pigments. Examples of inorganic pigments include yellow iron oxide, red iron oxide, titanium dioxide, and carbon black.

[0045] The above-mentioned colored paint composition preferably contains 0.5 to 60 parts by mass of the luminous agent and colored pigment in 100 parts by mass of the total solid content of the binder component, luminous agent and colored pigment.

[0046] (Other ingredients) Other components included in the colored paint composition, such as binder resins and crosslinking agents, include, for example, modified acrylic resins, polyester resins, epoxy resins, olefin resins, modified olefin resins, melamine resins, polyisocyanate compounds, and blocked isocyanate compounds. Furthermore, the solvent included in the colored paint composition can be one or more organic solvents commonly used in paints, such as ester-based, ether-based, alcohol-based, amide-based, ketone-based, aliphatic hydrocarbon-based, alicyclic hydrocarbon-based, and aromatic hydrocarbon-based solvents. However, when using the above solvents, if volatile substances remain in the laminated film, they may volatilize during decoration of the substrate, causing pinholes or blistering. Therefore, it is preferable to sufficiently reduce the amount of volatile substances contained in the laminated film.

[0047] (Design layer formed by printing (2)) The decorative laminated film of the present invention has a design layer (2) formed by printing. It may have the following properties. The printing method is not particularly limited and can be formed by known methods such as inkjet printing, screen printing, offset printing, or flexographic printing. In particular, inkjet printing is preferred because it can form various printed layers inexpensively. Furthermore, printing may be performed using energy ray curing ink.

[0048] (Metallic design layer (3)) The present invention provides a coating layer (3a) containing vapor-deposited aluminum or a vapor-deposited metal layer (3b) made of indium or tin, in order to obtain an excellent metallic appearance as if it were made of metal. By forming a metallic design layer such as (3a) or (3b) above, not only is a good metallic appearance obtained, but when stretching is performed during decoration of a three-dimensional molded product, cracks and whitening do not occur, and decoration with a good metallic appearance can be performed.

[0049] Since such metallic-looking design layers consist of a coating layer containing vapor-deposited aluminum (3a) or a vapor-deposited metal layer made of indium or tin (3b), these will be described in detail below.

[0050] (Coating layer containing vapor-deposited aluminum (3a)) The first example of a coating layer for forming a metallic-looking design layer in the present invention is one formed by a paint containing vapor-deposited aluminum pigment.

[0051] Such a coating layer (3a) containing vapor-deposited aluminum pigment can be, for example, formed by a metallic base coating containing 30 to 85% by weight of vapor-deposited aluminum pigment relative to the amount of solid content of the coating.

[0052] The above-mentioned vapor-deposited aluminum pigment is obtained by shredding a vapor-deposited aluminum film into flakes. Such non-leafing vapor-deposited aluminum pigments can be manufactured, for example, by using a plastic film such as oriented polypropylene, crystalline polypropylene, or polyethylene terephthalate as a base film, applying a release agent on it, and then vapor-depositing aluminum on top of the release agent.

[0053] Unlike conventional aluminum pigments such as aluminum flakes, the above-mentioned vapor-deposited aluminum pigment has less particle size, which makes it possible to provide a design layer with a mirror-like appearance similar to a metal surface.

[0054] The above-mentioned vapor-deposited aluminum pigment is more preferably a non-leafing vapor-deposited aluminum pigment. The non-leafing vapor-deposited aluminum pigment is preferably a particle size of 3 to 20 μm and a thickness of 0.01 to 0.1 μm. Having the above particle size makes it possible to obtain a new metallic design with less graininess. The above particle size is more preferably 5 to 15 μm. In this specification, the particle size is the value measured with a laser diffraction particle size distribution analyzer LA-910 (manufactured by Horiba, Ltd.). Examples of commercially available non-leafing vapor-deposited aluminum that can be used in the present invention include Metashen 11-0010, 41-0010, 71-0010, 91-0010, MS-750, MS-650 (manufactured by Ciba Specialty Co., Ltd.), and Silverline P1000, P4100, Metalure L, Metalure A21010BG (manufactured by Ekart Co., Ltd.).

[0055] Leafing treatment is a treatment applied to the surface of aluminum using hydrophobic and / or oleophobic agents. The non-leafing vapor-deposited aluminum pigment used in this invention is preferably a non-leafing vapor-deposited aluminum pigment that has not undergone such leafing treatment. When leafing vapor-deposited aluminum is used, the adhesion to adjacent coating layers decreases, resulting in adhesion problems. Therefore, in this invention, it is preferable to use non-leafing vapor-deposited aluminum.

[0056] The amount of the above-mentioned vapor-deposited aluminum pigment is 30 to 85% by weight relative to the total solid content of the coating layer (D-3a) containing the above-mentioned vapor-deposited aluminum. If the amount is less than 30% by weight, a glossy coating film that satisfies the dense metallic luster cannot be obtained, and if it exceeds 85% by weight, the physical properties of the coating film deteriorate. The content of the above-mentioned non-leafing vapor-deposited aluminum pigment is more preferably 40 to 80% by weight.

[0057] The coating layer (3a) containing the above-mentioned vapor-deposited aluminum further contains a binder resin in addition to the non-leafing vapor-deposited aluminum pigment. The binder resin is not particularly limited and can include vinyl chloride resin, acrylic resin, urethane resin, polyester resin, etc., and two or more of these may be used in mixture form. Among these, vinyl chloride resin is particularly preferred.

[0058] The vinyl chloride resin can be one that is available on the market. The vinyl chloride resin may be a homopolymer of vinyl chloride, or a copolymer of vinyl chloride with other vinyl monomers that can copolymerize with vinyl chloride. More specifically, the copolymer can be a copolymer of vinyl chloride with vinyl acetate, maleic anhydride or its esters, vinyl ether, acrylic acid, acrylic hydroxyl group-containing monomers, etc.

[0059] The degree of polymerization of these polyvinyl chloride resins is typically 200 to 2000, preferably 300 to 1000. Easily available commercially produced polyvinyl chloride resins include Solvine C, CN, A, TA2, TAO, TAOL, and M5 from Nisshin Chemical Industry; Vinnol H11 / 59, E15 / 48A, LL4320, and E15 / 45M from Wacker; and VYHD, VAGD, VMCH, and VMCC from Dow UCAR. Two or more of these can also be used in mixture form.

[0060] The coating layer (3a) containing the vapor-deposited aluminum may also contain an aluminum anti-coagulation agent. This is preferable because the action of the aluminum anti-coagulation agent can suppress cohesive failure between the aluminum and the resin. Specifically, Diana RE360 (manufactured by Mitsubishi Rayon Co., Ltd.) can be used as the aluminum anti-coagulation agent.

[0061] The coating layer (3a) containing the above-mentioned vapor-deposited aluminum may contain other luminous pigments and / or coloring pigments in addition to the above-mentioned specific non-leafing vapor-deposited aluminum pigment. Other luminous pigments and coloring pigments are not limited to those mentioned above, but include the luminous materials and coloring pigments described above.

[0062] The metallic base paint for forming the coating layer (3a) containing the above-mentioned vapor-deposited aluminum may contain, in addition to the above-mentioned components, polyethylene wax, settling inhibitors, curing catalysts, ultraviolet absorbers, antioxidants, leveling agents, surface modifiers such as silicones and organic polymers, anti-sagging agents, thickeners, defoaming agents, crosslinkable polymer particles (microgels), etc., as appropriate. The metallic base paint may be in the form of a solvent-based paint, a water-based paint, etc.

[0063] The coating layer (3a) containing the above-mentioned vapor-deposited aluminum preferably has a thickness of 0.05 to 5 μm. If it is outside this range, it is undesirable as it is prone to problems such as whitening and cracking.

[0064] (3b) A vapor-deposited metal layer consisting of indium or tin. First, let's explain the vapor-deposited metal layer. Vapor deposition is a method of forming a thin film by heating and vaporizing a deposition material in a vacuum container and depositing it onto the surface of a substrate placed at a distance. In this invention, the metals used for vapor deposition are tin and indium. Since vapor deposition requires a vacuum of approximately 10⁻³ to 10⁻⁴ Pa, the container must first be evacuated. Therefore, vapor deposition is a complete batch process and continuous processing is not possible.

[0065] Furthermore, the film deposition method generally consists of the following steps: (1) setting a film roll and target metal in a chamber, (2) evacuating the chamber (10⁻³ to 10⁻⁴ Pa) and starting the film to move, (3) heating the target and generating steam to deposit the film onto the surface, and (4) opening the chamber to the atmosphere when deposition is complete. Compared to direct deposition on parts, it is more economically efficient because an entire roll of film is processed continuously, even though it is a batch process. It also has the advantage of being easy to control the thickness and quality of the deposited film. However, it cannot be applied to three-dimensional shapes in its film form.

[0066] The vapor-deposited metal layer (3b) made of indium or tin in the present invention can be formed by a conventional vapor deposition method using these metals. By using indium or tin, a metal layer with good elongation properties can be obtained, so that cracking or whitening does not occur when forming into a three-dimensional shape, and the appearance is not adversely affected.

[0067] In this invention, by using indium or tin as the vapor-deposited metal layer, the discontinuous vapor deposition process has the advantage of making it less prone to cracking and whitening.

[0068] When forming such a vapor-deposited metal layer, its thickness is preferably 0.05 to 5 μm. This thickness allows for the successful achievement of the aforementioned objectives.

[0069] (Resin base layer) Examples of resin substrate layers according to the present invention include polyester films such as polycarbonate films, polyethylene terephthalate, and polyethylene naphthalate; cellulosic films such as diacetylcellulose and triacetylcellulose; and acrylic films such as polymethyl methacrylate (PMMA), which are made of resin substrates and have high transparency. Furthermore, the above-mentioned resin substrate layer may consist of resin substrates such as polystyrene, styrene-based films such as acrylonitrile-styrene copolymer; olefin-based films such as polyvinyl chloride, polyethylene, polypropylene, polyolefins having a cyclic or norbornene structure, ethylene-propylene copolymer; or amide-based films such as nylon and aromatic polyamide. Furthermore, the above-mentioned resin substrate layer may be made of a resin substrate such as polyimide, polysulfone, polyethersulfone, polyetheretherketone, polyphenylene sulfide, polyvinyl alcohol, polyvinylidene chloride, polyvinyl butyral, polyarylate, polyoxymethylene, epoxy resin, or a blend of the above polymers. Furthermore, the resin substrate layer may be a laminate of multiple resin substrates. For example, it may be a laminated member or sheet of a film made of acrylic resin and a film made of polycarbonate resin. As the above-mentioned resin substrate, at least one of polymethyl methacrylate (PMMA), polycarbonate (PC), and PMMA / PC is preferred due to its excellent weather resistance and shape stability, with PMMA being particularly preferred.

[0070] The above-mentioned resin substrate layer can be appropriately selected from among these resin substrates depending on the application, including those with low optical birefringence, those in which the phase difference is controlled to 1 / 4 (λ / 4) or 1 / 2 (λ / 2) of the wavelength (e.g., 550 nm), or those in which birefringence is not controlled at all.

[0071] The thickness of the resin substrate layer can be appropriately selected depending on the application of the decorative laminate and the processing method of the component. Generally, from the viewpoint of strength and workability such as handling, it is 50 μm to 400 μm, with 75 μm to 350 μm being particularly preferred, and 100 μm to 300 μm being more preferred.

[0072] (Other layers) The decorative laminated member of the present invention is based on the four layers described above: a heat-resistant film layer, an adhesive layer, a design layer, and a resin substrate layer. However, a clear coating layer may be formed after the resin substrate layer. The clear coating layer is often formed to keep the surface of the injection-molded product smooth and beautiful.

[0073] (Clear coating layer) The clear coating layer described above is not particularly limited and may be any known clear coating layer used in decorative laminate substrates, but it is preferable that it is obtained using an after-cure type clear coating layer forming composition described later.

[0074] (Composition for forming a clear coating layer) The clear coating layer comprises a composition for forming a clear coating layer. The composition for forming a clear coating layer according to the present invention has unreacted (meth)acryloyl groups. Furthermore, the clear coating layer formed by applying the clear coating layer-forming composition, for example, the clear coating layer of an unheated sample, has unreacted (meth)acryloyl groups. Furthermore, when the heated sample is irradiated with an active energy ray of 500 mJ / cm2, the unreacted (meth)acryloyl groups in the clear coating layer are 10-100% gone compared to the unreacted (meth)acryloyl groups in the clear coating layer of the unheated sample. A clear coating layer-forming composition having such a relationship allows the crosslinking density to be set within a desired range, and the hard coat layer formed by curing the clear coating layer can have excellent physical properties. For example, it is possible to obtain a molded product that has excellent abrasion resistance and chemical resistance, as well as high hardness. Such clear coating layers and compositions for forming clear coating layers can achieve, for example, the effects described below.

[0075] The clear coating layer forming composition used in forming the clear coating layer according to the present invention is preferably a radiation-curable clear coating layer forming composition from the viewpoint of obtaining excellent hardness. Among these, an active energy ray-curable clear coating layer forming composition is more preferable.

[0076] The active energy ray curable clear coating layer forming composition may be dried at, for example, 80°C to 120°C before curing or semi-curing. Furthermore, with the active energy ray curable clear coating layer formation composition according to the present invention, the protective film layer, the clear coating layer, and the resin substrate can be wound up in this order, and for example, air can be trapped between the protective film layer and the clear coating layer.

[0077] For example, the clear coating layer according to the present invention, which includes an active energy ray curable clear coating layer forming composition, can significantly suppress defects caused by external stress that may occur during the formation of a design layer, such as printing on a resin substrate. For example, defects such as dents and scratches can be suppressed, making it possible to obtain molded products with an excellent appearance.

[0078] Furthermore, the clear coating layer according to the present invention is preferable in that it can suppress curling, lifting, etc., caused by differences in thermal shrinkage between the protective film layer and the resin substrate. Moreover, even when complex shapes are given to the decorative laminated member of the present invention during the preforming process, etc., cracks, changes in appearance, foaming, etc., do not occur.

[0079] (Resin components) The active energy ray-curable clear coating layer formation composition contains a resin component that forms the clear coating layer. Preferably, this resin component contains an active energy ray-curable component. Active energy ray curable components are monomers, oligomers, or polymers (also called resins) that can be crosslinked and cured by active energy rays (e.g., ultraviolet light). Specific examples of such active energy ray curable components include monomers, oligomers, or polymers having at least one unsaturated double bond group, more specifically, (meth)acrylate monomers, (meth)acrylate oligomers, (meth)acrylate polymers, urethane (meth)acrylate monomers, urethane (meth)acrylate oligomers, urethane (meth)acrylate polymers, silicon (meth)acrylate, and modified monomers, oligomers, and polymers thereof, all having at least one unsaturated double bond group. These monomers, oligomers, and polymers may also be used in combination. Note that "(meth)acrylate" refers to acrylate and / or methacrylate. In one embodiment, the active energy ray curable clear coating layer forming composition contains an unsaturated double bond-containing acrylic resin (also called an unsaturated double bond-containing acrylic polymer). In one embodiment, the clear coating layer-forming composition may include a non-reactive acrylic resin. Furthermore, the clear coating layer-forming composition may include an unsaturated double-bond-containing acrylic resin and / or a non-reactive acrylic resin. The clear coating layer-forming composition may, for example, contain multiple types of unsaturated double bond-containing acrylic resins and / or non-reactive acrylic resins.

[0080] For example, an active energy ray curable component, such as a clear coating layer forming composition, includes an unsaturated double bond-containing acrylic resin and / or a non-reactive acrylic resin having a weight-average molecular weight (Mw) of 5,000 to 100,000. In one embodiment, the unsaturated double bond-containing acrylic resin and / or the non-reactive acrylic resin may have a weight-average molecular weight (Mw) of 5,000 to 100,000, for example, a weight-average molecular weight (Mw) of 6,000 to 95,000. The weight-average molecular weight (Mw) can be calculated by known methods.

[0081] In another embodiment, when the active energy ray curable component includes multiple types of polymers, one polymer may have a weight-average molecular weight (Mw) of 5,000 to 100,000, and another polymer may have a weight-average molecular weight (Mw) of 10,000 to 80,000. Furthermore, polymers having different ranges of weight-average molecular weight (Mw) may be included. By using polymers with various weight-average molecular weight ranges in combination, the clear coating layer can exhibit various properties such as high smoothness and high rigidity in the uncured state. Furthermore, the hard coat layer obtained by curing the clear coating layer can also have high smoothness and excellent hard coat performance, such as high hardness, abrasion resistance, and chemical resistance.

[0082] While it should not be interpreted in isolation from any particular theory, the inclusion of an unsaturated double-bond-containing acrylic resin and / or a non-reactive acrylic resin can increase the rigidity of the uncured clear coating layer. Furthermore, by including at least one selected from the group consisting of polyfunctional (meth)acrylates and polyfunctional urethane (meth)acrylates, the crosslinking density of the hard coat layer cured from the clear coating layer can be maintained, allowing the clear coating layer to have high viscosity at room temperature. Moreover, heating can lead to lower viscosity and excellent moldability. As a result, it becomes possible to mold even more complex shapes, further reduce the occurrence of defective products during molding, and the resulting molded articles can have superior hard coat performance, such as higher hardness, wear resistance, and chemical resistance.

[0083] In one embodiment, the clear coating layer-forming composition comprises an unsaturated double bond-containing acrylic resin and / or a non-reactive acrylic resin, and at least one selected from the group consisting of polyfunctional (meth)acrylates and polyfunctional urethane (meth)acrylates. For example, the clear coating layer-forming composition comprises an unsaturated double bond-containing acrylic resin and / or a non-reactive acrylic resin having a weight-average molecular weight (Mw) of 5,000 to 100,000, and at least one selected from the group consisting of polyfunctional (meth)acrylates with an acrylate equivalent of 50 to 500 and polyfunctional urethane (meth)acrylates with an acrylate equivalent of 50 to 500.

[0084] In this specification, a non-reactive acrylic resin is an acrylic resin that does not react or shows little to no reaction when irradiated with active energy rays, for example, an acrylic resin that does not react or shows little to no reaction when irradiated with ultraviolet light.

[0085] The acrylate equivalents of the above-mentioned polyfunctional (meth)acrylate and polyfunctional urethane (meth)acrylate are, for example, 50 to 500, for example, 60 to 400, in another embodiment, 70 to 350, and in yet another embodiment, 100 to 200. By including such a polyfunctional (meth)acrylate and / or polyfunctional urethane (meth)acrylate with the acrylic resin described above, it is possible to further suppress air entrapment and obtain a clear coating layer free from dust, scratches, etc. Furthermore, even with complex shapes, it is possible to obtain molded products with an excellent appearance without defects such as cracks. In addition, molded products can be obtained that have excellent wear resistance and chemical resistance, as well as high hardness.

[0086] In one embodiment, the composition for forming a clear coating layer comprises an unsaturated double bond-containing acrylic resin and / or a non-reactive acrylic resin, a polyfunctional silicone (meth)acrylate, a fluororesin, and inorganic oxidized fine particles. For example, a composition for forming a clear coating layer includes an unsaturated double bond-containing acrylic resin and / or a non-reactive acrylic resin, a polyfunctional silicon (meth)acrylate having a weight-average molecular weight (Mw) of 700 to 100,000, a fluororesin, and inorganic oxidized fine particles. While it should not be interpreted in isolation from any particular theory, the inclusion of polyfunctional silicon (meth)acrylate enables lower surface tension, excellent leveling properties, and reduced tack. Furthermore, the inclusion of fluororesin imparts slipperiness to the clear coating layer (coating). Additionally, the inclusion of inorganic oxidized fine particles provides excellent abrasion resistance and reduces tack.

[0087] The weight-average molecular weight (Mw) of the polyfunctional silicon (meth)acrylate is, for example, 700 to 100,000, in one embodiment it is 800 to 90,000, and in another embodiment it is 800 to 85,000.

[0088] In one embodiment, the fluorine content of the fluororesin is 5% by weight or more and 80% by weight or less, for example, 5% by weight or more and 75% by weight or less.

[0089] For example, a clear coating layer-forming composition contains, per 100 parts by mass of the solid content in the composition, an amount of unsaturated double bond-containing acrylic resin and / or non-reactive acrylic resin in an amount greater than 20 parts by mass and / or 60 parts by mass or less, for example, 30 parts by mass or more and 60 parts by mass or less, and in one embodiment, 35 parts by mass or more and 60 parts by mass or less. When a clear coating layer-forming composition contains multiple types of unsaturated double bond-containing acrylic resins and / or non-reactive acrylic resins, it is preferable that the total amount of multiple types of unsaturated double bond-containing acrylic resins and / or non-reactive acrylic resins is within the above range. In this invention, 100 parts by mass of solids contained in the composition means that the total of the resin solids, such as the unsaturated double bond-containing acrylic resin and / or non-reactive acrylic resin, polyfunctional (meth)acrylate, polyfunctional urethane (meth)acrylate, polyfunctional silicone (meth)acrylate, fluororesin, and photopolymerization initiator, and the solids of the inorganic oxidized fine particles, if present, equals 100 parts by mass.

[0090] In one embodiment, the clear coating layer forming composition contains 5 to 70 parts by mass, for example, 10 to 70 parts by mass, of polyfunctional (meth)acrylate and / or polyfunctional urethane (meth)acrylate per 100 parts by mass of solids contained in the composition, and in another embodiment, 13 to 68 parts by mass.

[0091] In one embodiment, the clear coating layer forming composition contains 5 to 50 parts by mass, for example, 10 to 48 parts by mass, of polyfunctional silicone (meth)acrylate per 100 parts by mass of solids contained in the composition, and in another embodiment, 15 to 48 parts by mass.

[0092] In one embodiment, the clear coating layer forming composition contains 0.1 parts by mass to 10 parts by mass of fluororesin, for example, 1 part by mass to 8 parts by mass, per 100 parts by mass of solids contained in the composition, and in another embodiment, 1.5 parts by mass to 7 parts by mass.

[0093] In one embodiment, the clear coating layer forming composition contains 1 to 55 parts by mass, for example, 10 to 50 parts by mass, of inorganic oxidized fine particles per 100 parts by mass of solid content in the composition, and in another embodiment, 12 to 40 parts by mass. By including inorganic oxide fine particles within this range in a clear coating layer formation composition, rigidity can be imparted to the uncured coating film, for example, resulting in a better coating appearance. The appearance of the resulting molded product can be maintained well. Furthermore, the abrasion resistance of the cured coating film can be improved.

[0094] In one embodiment, the clear coating layer-forming composition in the unirradiated state of active energy rays is a composition in which the molecular weight distribution shape does not change before and after heating for 30 to 60 seconds in an atmosphere of 150 to 190°C. For example, the coating composition contained in the clear coating layer of the heated sample (1) for stretching test, which is a sample before irradiation with active energy rays, is a composition in which the molecular weight distribution shape does not change before and after heating for 30 to 60 seconds in an atmosphere of 150 to 190°C. Here, "no change in the shape of the molecular weight distribution" means that, for the weight-average molecular weight peak, or each molecular weight peak if there are multiple quantitative peaks, the height shift and lateral shift of each molecular weight peak before and after heating for 30 to 60 seconds in an atmosphere of 150 to 190°C are both within the range of ±5%.

[0095] The clear coating layer forming composition according to the present invention can increase the crosslinking density after curing, enhance the effect of improving surface hardness, and enhance the effect of improving transparency, Polyfunctional (meth)acrylate compounds such as polyfunctional (meth)acrylate monomers, polyfunctional (meth)acrylate oligomers, or polyfunctional (meth)acrylate polymers (in this specification, polyfunctional (meth)acrylate compounds may be abbreviated as "polyfunctional (meth)acrylate"); Polyfunctional urethane (meth)acrylate compounds such as polyfunctional urethane (meth)acrylate monomers, polyfunctional urethane (meth)acrylate oligomers, and polyfunctional urethane (meth)acrylate polymers (in this specification, polyfunctional urethane (meth)acrylate compounds may be abbreviated as "polyfunctional urethane (meth)acrylate"); Polyfunctional silicone (meth)acrylate compounds such as polyfunctional silicone (meth)acrylate monomers, polyfunctional silicone (meth)acrylate oligomers, and polyfunctional silicone (meth)acrylate polymers (in this specification, polyfunctional silicone (meth)acrylate compounds may also be abbreviated as "polyfunctional silicone (meth)acrylate"); Preferably, it contains at least one selected from polyfunctional (meth)acrylate compounds, polyfunctional urethane (meth)acrylate compounds, and polyfunctional silicone (meth)acrylate compounds.

[0096] Commercially available (meth)acrylate monomers or oligomers having one unsaturated double bond group may be used. Examples of commercially available products include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, acrylic acid, methacrylic acid, isostearyl (meth)acrylate, ethoxylated o-phenylphenol acrylate, methoxypolyethylene glycol acrylate, methoxypolyethylene glycol acrylate, phenoxypolyethylene glycol acrylate, 2-acryloyloxyethyl succinate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, ethylene glycol mono(meth)acrylate, propylene glycol mono(meth)acrylate, 2-hydroxy-3-methoxypropyl (meth)acrylate, N-methylol(meth)acrylamide, and N-hydroxy(meth)acrylamide.

[0097] The polyfunctional (meth)acrylate monomer or oligomer may be modified as necessary. However, in this specification, neither "polyfunctional urethane (meth)acrylate" nor "polyfunctional silicone (meth)acrylate" is included in "polyfunctional (meth)acrylate".

[0098] Commercially available products may be used as polyfunctional (meth)acrylate monomers or oligomers. Examples of commercially available products include DPHA (manufactured by Daicel Ornex), PETRA (manufactured by Daicel Ornex: pentaerythritol triacrylate), PETIA (manufactured by Daicel Ornex), Aronics M-403 (manufactured by Toagosei Co., Ltd.: dipentaerythritol penta and hexaacrylate), Aronics M-402 (manufactured by Toagosei Co., Ltd.: dipentaerythritol penta and hexaacrylate), Aronics M-400 (manufactured by Toagosei Co., Ltd.: dipentaerythritol penta and hexaacrylate), SR-399 (manufactured by Arkema: dipentaerythritol hydroxypentaacrylate), KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.), KAYARAD DPHA-2C (manufactured by Nippon Kayaku Co., Ltd.), Aronics M-404, M-405, M-406, M-450, M-305, M-309, M-310, M-315, M-320, TO-1200, TO-1231, TO-595, TO-756 (all manufactured by Toagosei Co., Ltd.), KAYARD Products such as D-310, D-330, DPHA, DPHA-2C (all manufactured by Nippon Kayaku Co., Ltd.), Nikalac MX-302 (manufactured by Sanwa Chemical Co., Ltd.), A-9300, A-9300-1CL, A-GLY-9E, A-GLY-20E, A-TMM-3, A-TMM-3L, A-TMM-3LM-N, A-TMPT, AD-TMP, ATM-35E, A-TMMT, A-9550, and A-DPH (all manufactured by Shin Nakamura Chemical Industry Co., Ltd.) can be used.

[0099] Examples of monofunctional or polyfunctional (meth)acrylate polymers include high molecular weight compounds of the above-mentioned monofunctional or polyfunctional (meth)acrylate monomers or oligomers.

[0100] In this specification, the various polymers described above may be simply referred to as unsaturated double bond-containing acrylic polymers or unsaturated double bond-containing acrylic resins.

[0101] Commercially available products may be used as polyfunctional urethane (meth)acrylate monomers or oligomers. Commercially available products include, for example, bifunctional urethane (meth)acrylate ("UX-2201", "UX-8101", "UX-6101" from Nippon Kayaku Co., Ltd., "UF-8001", "UF-8003" from Kyoeisha Chemical Co., Ltd., and "Ebecryl244", "Ebecryl284", "Ebecryl2002", "Ebecryl4835", "Ebecryl4883", "Ebecryl8807", "Ebecryl6700" from Daicel Ornex Co., Ltd.), trifunctional urethane (meth)acrylate ("Ebecryl254", "Ebecryl264", "Ebecryl265" from Daicel Ornex Co., Ltd.), tetrafunctional urethane (meth)acrylate ("Ebecryl8210" from Daicel Ornex Co., Ltd.), and hexafunctional urethane (meth)acrylate (Daicel Ornex's "Ebecryl1290k", "Ebecryl5129", "Ebecryl220", "KRM8200", "Ebecryl1290N"), 9-functional urethane (meth)acrylate (Daicel Ornex's "KRM7804"), 10-functional urethane (meth)acrylate (Daicel Ornex's "KRM8452", "KRM8509"), 15-functional urethane (meth)acrylate (Daicel You can use "KRM8655" from Ornex Co., Ltd., and Art Resin UN-3320HA, Art Resin UN-3320HB, Art Resin UN-3320HC, Art Resin UN-3320HS, Art Resin UN-904, Art Resin UN-901T, Art Resin UN-905, Art Resin UN-952 (all from Negami Kogyo Co., Ltd.), U-6HA, U-15HA, UA-100H, U-4HA, U-6LPA, UA-32P, U-324A, U-4H (all from Shin Nakamura Chemical Co., Ltd.).

[0102] Monofunctional or polyfunctional urethane (meth)acrylate monomers or oligomers can also be prepared, for example, by reacting a polycarbonate diol with a (meth)acrylate compound containing a hydroxyl group and an unsaturated double bond group in the molecule and a polyisocyanate.

[0103] Examples of monofunctional or polyfunctional urethane (meth)acrylate polymers include high molecular weight compounds of the above-mentioned monofunctional or polyfunctional urethane (meth)acrylate monomers or oligomers.

[0104] Polyfunctional silicone (meth)acrylate monomers or oligomers are compounds having a silicone skeleton. For example, a compound having a silicone skeleton may have a fluorine atom-containing group, and a fluororesin may have a silicone skeleton. Commercially available polyfunctional silicon (meth)acrylate monomers or oligomers may be used. Examples of commercially available products include the following: Compounds having methacryloyl and acryloyl groups BYK Corporation: BYK-UV3500, BYK-UV3570 Manufactured by Shin-Etsu Chemical Co., Ltd.: Shin-Etsu Silicone X-22-164, Shin-Etsu Silicone X-22-164AS, Shin-Etsu Silicone X-22-164A, Shin-Etsu Silicone X-22-164B, Shin-Etsu Silicone X-22-164C, Shin-Etsu Silicone X-22-164E, Shin-Etsu Silicone X-22-174DX, Shin-Etsu Silicone X-22-2426, Shin-Etsu Silicone X-22-2475, KER-4000-UV, KER-4700-UV, KER-4710-UV, KER-4800-UV, JNC Corporation models: FM-0711, FM-0721, FM-0725, TM-0701, FM-7711, FM-7721, FM-7725 Evonik Japan: TEGO® Rad 2010, TEGO® Rad 2011. Materials containing fluorine atoms and (meth)acryloyl groups, and materials having a fluororesin compound with a silicone backbone. Manufactured by Nippon Gosei Kagaku Kogyo Co., Ltd.: Shikou UV-AF305 T&K TOKA: ZX-212, ZX-214-A Examples include KY-1203 manufactured by Shin-Etsu Chemical Co., Ltd.

[0105] The active energy ray curable clear coating layer forming composition may also contain, for example, a fluororesin in addition to the resin described above. The inclusion of a fluororesin in the composition can further improve the wear resistance of the molded product. In the present invention, the term "fluororesin" refers to a fluorine-containing resin that does not contain a silicone skeleton compound. Examples include perfluorooctyl acrylate and acrylic-modified perfluoropolyether. The fluorine-containing resin may have modified methacryloyl and acryloyl functional groups. The fluororesin may be, for example, one of the following commercially available products. DIC Corporation products: MegaFuck RS-72-K, MegaFuck RS-75, MegaFuck RS-76-E, MegaFuck RS-76-NS, MegaFuck RS-77 Daikin Industries, Ltd.: Optool DAC-HP Solvay Solexis: FLUOROLINK MD700, FLUOROLINK AD1700 Neos Corporation products: such as Futergent 601ADH2.

[0106] Furthermore, the clear coating layer-forming composition does not tack in its uncured state, and the clear coating layer can suppress the adhesion of dust. In addition, it can suppress or significantly reduce the occurrence of appearance defects in the clear coating layer when the protective film layer is peeled off.

[0107] In one embodiment, the clear coating layer forming composition includes inorganic oxidized fine particles. The inorganic oxidized fine particles may be inorganic oxidized fine particles whose surface is modified with unsaturated double bonds. Examples of inorganic oxide fine particles include silica (SiO2) particles, alumina particles, titania particles, tin oxide particles, antimond-doped tin oxide (ATO) particles, and zinc oxide particles. Among these, silica particles and alumina particles are preferable from the viewpoint of cost and paint stability, and those with modified functional groups are even more desirable. The functional group is preferably a (meth)acryloyl group. For example, the primary particle size of inorganic oxide fine particles is 5 nm to 100 nm from the viewpoint of transparency and paint stability. In this specification, the average particle size of granular material is a value measured from images of a cross-sectional electron microscope using image processing software. For example, by incorporating inorganic oxide fine particles, volume shrinkage of the uncured coating film can be mitigated. Furthermore, by incorporating inorganic oxide fine particles, in addition to the above effect, rigidity can be imparted to the coating film. Furthermore, by incorporating inorganic oxide fine particles, it is possible to suppress the occurrence of curling due to curing shrinkage in the cured coating film. For example, by incorporating inorganic oxide fine particles, in addition to the above effects, wear resistance can be provided.

[0108] For example, commercially available inorganic oxide fine particles may be used, such as silica particles (colloidal silica) manufactured by Nissan Chemical Industries: IPA-ST, MEK-S™, IBK-S T, PGM-ST, XBA-S T, MEK-A2101, MEK-A2202, MEK-AC-4101M, IBK-SD. Manufactured by Fuso Chemical Industry Co., Ltd.: PL-1-IPA, PL-1-TOL, PL-2-IPA PL-2-MEK, PL-3-TOL JGC Catalysts & Chemicals Co., Ltd.: OSCAL series, ELECOM series Examples include the NANOBYK-3605 manufactured by Big Chemie Japan. For example, as alumina particles, Sumitomo Osaka Cement Co., Ltd.: AS-150I, AS-150T Examples of products manufactured by Big Chemie Japan include NANOBYK-3601, NANOBYK-3602, and NANOBYK-3610.

[0109] (Photopolymerization initiator) The clear coating layer-forming composition of the present invention preferably contains a photopolymerization initiator. The presence of a photopolymerization initiator allows the resin component to polymerize well when exposed to active energy rays, such as ultraviolet light. Examples of photopolymerization initiators include alkylphenone-based photopolymerization initiators, acylphosphine oxide-based photopolymerization initiators, titanocene-based photopolymerization initiators, oxime ester-based polymerization initiators, and intramolecular hydrogen abstraction type photopolymerization initiators. Examples of alkylphenone-based photopolymerization initiators include 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propane-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)-benzyl]phenyl}-2-methylpropane-1-one, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, and 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone. Examples of acylphosphine oxide-based photopolymerization initiators include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide. Examples of titanocene-based photopolymerization initiators include bis(η5-2,4-cyclopentadiene-1-yl)-bis(2,6-difluoro-3-(1H-pyrrole-1-yl)-phenyl)titanium. Examples of oxime ester polymerization initiators include 1,2-octanedione,1-[4-(phenylthio)-,2-(O-benzoyl oxime)], ethanone,1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-,1-(O-acetyl oxime), oxyphenylacetic acid, 2-[2-oxo-2-phenylacetoxyethoxy]ethyl ester, and 2-(2-hydroxyethoxy)ethyl ester.Examples of intramolecular hydrogen abstraction type photopolymerization initiators include benzophenone, methyl benzoyl formate, and ketocoumarin. These photopolymerization initiators may be used individually or in combination of two or more.

[0110] Among the above photopolymerization initiators, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, and 2,2-dimethoxy-1,2-diphenylethane-1-one are more preferably used.

[0111] The preferred amount of photopolymerization initiator is 0.01 to 10 parts by mass per 100 parts by mass of the solid content of the clear coating layer forming composition, for example, 1 to 10 parts by mass. The photopolymerization initiator may be used alone, or two or more photopolymerization initiators may be used in combination.

[0112] (solvent) The clear coating layer-forming composition may contain a solvent. The solvent is not particularly limited and can be selected as appropriate, taking into consideration the components contained in the composition, the type of substrate to be coated, and the method of application of the composition. Specific examples of solvents that can be used include, for example, aromatic solvents such as toluene and xylene; ketone solvents such as methyl ethyl ketone, acetone, methyl isobutyl ketone, and cyclohexanone; ether solvents such as diethyl ether, isopropyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, anisole, and phenethole; ester solvents such as ethyl acetate, butyl acetate, isopropyl acetate, and ethylene glycol diacetate; amide solvents such as dimethylformamide, diethylformamide, and N-methylpyrrolidone; cellosolve solvents such as methyl cellosolve, ethyl cellosolve, and butyl cellosolve; alcohol solvents such as methanol, ethanol, propanol, isopropyl alcohol, butanol, and isobutyl alcohol; and halogen solvents such as dichloromethane and chloroform. These solvents may be used individually or in combination of two or more. Of these solvents, ester-based solvents, ether-based solvents, alcohol-based solvents, and ketone-based solvents are preferably used.

[0113] The clear coating layer forming composition may contain various additives as needed. Examples of such additives include commonly used additives such as antistatic agents, plasticizers, surfactants, antioxidants, UV absorbers, light stabilizers, surface modifiers, and leveling agents. The inclusion of these additives in the clear coating layer forming composition offers the advantage of further improving the durability of decorative molded members and decorative molded articles. These additives can be those commonly used in the field of clear coating layer formation.

[0114] A composition for forming a clear coating layer can be prepared by methods commonly used by those skilled in the art. For example, it can be prepared by mixing the above-mentioned components using commonly used mixing equipment such as a paint shaker or mixer.

[0115] (Protective film layer) The decorative laminated member of the present invention may further have a protective film layer. The protective film layer may or may not be peeled off.

[0116] The resin film that can be applied to the substrate of the protective film layer is not particularly limited. For example, it may be a polyolefin film such as polyethylene film and polypropylene film, a modified polyolefin film obtained by modifying these polyolefins and adding further functions, a polyester film such as polyethylene terephthalate, polycarbonate and polylactic acid, a polystyrene film, a polystyrene-based resin film such as AS resin film and ABS resin film, a nylon film, a polyamide film, a polyvinyl chloride film and a polyvinylidene chloride film, a polymethylpentene film, or any other film. Furthermore, if necessary, additives such as antistatic agents and UV inhibitors can be applied, and the surface of the substrate can be treated with corona treatment or low-temperature plasma treatment.

[0117] In one embodiment, the resin film applicable to the substrate of the protective film layer is at least one film selected from polyethylene film, polystyrene film, modified polyolefin film, polymethylpentene film, unoriented polypropylene film (CPP film), and biaxially oriented polypropylene film (OPP film). In another embodiment, the resin film that can be applied to the substrate of the protective film layer is a polypropylene film, for example, an oriented polypropylene film (OPP film) or an unoriented polypropylene film (CPP film). The thickness of the protective film layer is not particularly limited, but it is preferably 10 μm at the lower limit and 100 μm at the upper limit, and more preferably 20 μm at the lower limit and 80 μm at the upper limit.

[0118] Furthermore, an adhesive layer may be provided between the protective film layer and the clear coating layer as needed. Having an adhesive layer on the protective film layer helps maintain the conformability and adhesion of the protective film layer to the clear coating layer, better protecting the uncured clear coating layer from external factors (e.g., scratches caused by the equipment) and suppressing air trapped in the coating. Furthermore, even when winding up the uncured clear coating layer and the protective film layer, such problems can be prevented or significantly reduced.

[0119] (Method of manufacturing decorative laminated material) Each layer other than the resin substrate layer that constitutes the decorative laminated member of the present invention can be formed by preparing a paint composition in which the components constituting each layer are dissolved in a solvent, and then applying and drying this on the resin substrate layer. Furthermore, if a protective film layer is provided, a laminated structure can be obtained by laminating the protective film layer onto the laminated member formed in this manner.

[0120] The coating method for forming each of the above layers is not particularly limited, but for example, it may be applied by spraying, or by using an applicator, die coater, bar coater, roll coater, comma coater, roller brush, brush, spatula, etc. After applying the paint solution using the above coating method, the layers can be formed by heating and drying to remove the solvent in the paint solution.

[0121] The heating and / or irradiation with active energy rays to cure each of the above layers may be performed sequentially for each layer after the layer is formed, or the heating and / or irradiation with energy rays may be performed after the entire laminated structure has been formed. However, it is preferable to perform the heating and / or irradiation with energy rays after the preforming process to cure the layers (after-cure).

[0122] Furthermore, as mentioned above, the adhesive layer may be bonded by lamination rather than by coating and drying. That is, a film formed by the adhesive layer may be prepared and then bonded to the film by lamination.

[0123] (How to use) When decorating a molded product using the decorative laminated substrate of the present invention, the method may be the same as conventionally known methods and is not particularly limited. That is, if necessary, the protective film layer may be peeled off from the decorative laminated member, and the decorative laminated member may be pressed firmly onto the substrate so that the heat-resistant film layer faces the substrate surface. After that, electromagnetic wave irradiation or heating may be performed to cure each layer and obtain a coating film. Alternatively, the protective film layer may be peeled off after pressing and curing. When adhering the decorative laminated member to the substrate surface, vacuum / pressure forming, vacuum forming, injection molding, heating and molding, etc. can be performed, but it can be suitably used in insert molding.

[0124] The present invention also relates to a decorative molded product comprising the above-mentioned decorative laminated member and resin molded body. The method for manufacturing the decorative molded product of the present invention is not particularly limited, but it is preferably obtained by the following insert molding method. The decorative laminated member is pre-molded to fit a predetermined injection molding die, the shaped decorative laminated member is placed in the injection molding die, the injection molding die is closed, molten resin is injected into the injection molding die, and the cooled and solidified resin and the decorative laminated member are integrated. Finally, after the molten resin has cooled and solidified, the injection molding die is opened, and the insert molded product, whose surface is covered with the decorative laminated member, is removed from the injection molding die.

[0125] The resin used in the above-mentioned molded resin is not particularly limited and includes, for example, acrylonitrile styrene resin, acrylonitrile butadiene styrene resin, polycarbonate resin, polystyrene resin, acrylic resin, polyester resin, polypropylene resin, olefin-based elastomer resin, etc. In particular, to further enhance recyclability, it is preferable that the resin used in the above-mentioned molded resin is the same resin as the heat-resistant film layer.

[0126] The resin molded articles that can be suitably decorated with the decorative laminated member of the present invention are not particularly limited, but examples include automotive exterior parts such as bumpers, front under spoilers, rear under spoilers, side under skirts, side garnishes, and door mirrors; automotive interior parts such as instrument panels, center consoles, and door switch panels; housings for home appliances such as mobile phones, audio products, refrigerators, fan heaters, and lighting fixtures; and washbasins. [Examples]

[0127] The present invention will be described below with reference to examples. In the examples, percentages in the formulation ratios refer to weight percentages unless otherwise specified. The present invention is not limited to the examples described below.

[0128] (Adhesive for forming adhesive layers) The following adhesive was used. Adhesive 1: Alkali-removable prototype adhesive 3 (manufactured by Toyo Morton Co., Ltd.) Adhesive 2: Alkali-removable prototype adhesive 1 (manufactured by Toyo Morton Co., Ltd.) Adhesive 3: Alkali-removable prototype adhesive 2 (manufactured by Toyo Morton Co., Ltd.)

[0129] (Preparation of composition for forming a clear coating layer) A clear coating layer composition 1 with a solid content of 35% was prepared by mixing 15 parts by mass of KRM-8452 (manufactured by Daicel Ornex Co., Ltd., polyfunctional urethane acrylate 1) as an active energy ray curable component, 40 parts by mass of Unidick V-6850 (manufactured by DIC Corporation, unsaturated double bond-containing acrylic resin), 40 parts by mass of Shiko UV-AF305 (manufactured by Mitsubishi Chemical Corporation, polyfunctional urethane acrylate), and 5 parts by mass of a photopolymerization initiator (product name: Omnirad184, manufactured by IGM RESINS) in a container containing 130 parts of methyl isobutyl ketone.

[0130] (Preparation of coating compositions for decorative layers) In a container containing methyl isobutyl ketone, 90 parts by mass of Kotax A228 (manufactured by Toray Fine Chemicals Co., Ltd.) as an acrylic resin, 9 parts by mass of aluminum paste 07-0674 (Toyo Aluminum Co., Ltd.) as a glossing agent, and Disparon 6901-20X (manufactured by Kusumoto Chemicals Co., Ltd., an anti-settlement agent for aluminum pigments) as an additive were mixed to produce a coating composition 1 for decorative layers with a solid content of 30%.

[0131] The resin substrate and heat-resistant film used are as follows: Resin base material 1: Parapure HI-001 (manufactured by Kuraray Co., Ltd., acrylic resin film, thickness 125 μm) Heat-resistant film 1: TP23030A (manufactured by Okamoto Co., Ltd., polypropylene resin film, 400 μm thickness) Heat-resistant film 2: PP sheet, white (manufactured by Shinwa Co., Ltd., polypropylene resin film, 250 μm thickness) Heat-resistant film 3: PP backer sheet (manufactured by Nippon Matai Co., Ltd., polypropylene resin film, 100 μm thickness)

[0132] <Example 1 and Comparative Examples 1 and 2> A coating composition 1 for the decorative layer was applied to a resin substrate 1 using an applicator so that a decorative layer with a dry film thickness of 20 μm was obtained, and then dried at 80°C for 5 minutes to form the decorative layer.

[0133] Next, one side of the heat-resistant film was subjected to corona treatment. Then, each adhesive was applied to the corona-treated surface using an applicator to obtain adhesive layers of each dry thickness, dried at 80°C for 1 minute, and the side with the design layer of the film having the resin substrate layer and design layer obtained in the above process was laminated at 100°C. The resulting film was cured at 40°C for 3 days to obtain a decorative laminated member.

[0134] <Examples 2-5> The clear coating composition 1 is applied to the resin substrate 1 using a bar coater to obtain a clear coating layer with a dry film thickness of 20 μm, dried at 80°C for 2 minutes, and then subjected to an integrated light intensity of 2000 mJ / cm². 2 The resin substrate layer was irradiated with UV light to form a clear coating layer. Next, the coating composition 1 for the design layer was applied using an applicator to the side of the resin substrate layer opposite to the clear coating layer, so that a design layer with a dry film thickness of 20 μm was obtained. After that, it was dried at 80°C for 5 minutes to form the design layer.

[0135] Next, corona treatment was applied to one side of each heat-resistant film. Then, each adhesive was applied to the corona-treated surface using an applicator to obtain an adhesive layer with a dry film thickness of 15 μm. The adhesive was dried at 80°C for 1 minute, and the side with the design layer of the film having the clear coating layer, resin substrate layer, and design layer obtained in the above process was laminated at 100°C. The resulting film was cured at 40°C for 3 days to obtain a decorative laminated member.

[0136] The following evaluations were performed on the obtained decorative laminated members. (Measurement of displacement) A holding strength test was performed at 80°C on the decorative laminated members obtained in each example and comparative example, and the amount of displacement after 24 hours was measured. This will be explained with reference to Figure 2. Figure 2 schematically shows the method of measuring the amount of displacement. The leftmost figure is a view from above when the decorative laminated member is laid flat, the middle figure schematically shows the initial state of the cross-section of the decorative laminated member passing through the metal rod, and the rightmost figure schematically shows the middle figure after 24 hours at 80°C. For each decorative laminated member cut to a width of 25 mm and a length of 125 mm as shown in the leftmost figure, a cut was made with a cutter at a position 25 mm from one end in the length direction (125 mm is the length direction), so as to reach the heat-resistant film layer from the surface on the resin substrate layer side. Next, a hole was made on the other end of each decorative laminated member, a rod-shaped metal (indicated as a metal rod in the middle figure) was passed through the hole, and each decorative laminated member was suspended vertically from the ground. Subsequently, a 1 kg load (1 kg load applied with a weight in Figure 2) was applied to the resin substrate layer surface on the side with the cut, and the sample was left in an 80°C constant temperature bath for 24 hours. The amount of displacement at the cut portion before and after the 24-hour period (in the rightmost diagram of Figure 2, the unit is mm in the space labeled "displacement") was measured. The results are shown in Table 1.

[0137] (Measurement of peel strength) Each decorative laminate obtained in each example and comparative example was cut into 15 mm wide strips, and a cutter was inserted at one end of the strip at the interface between the adhesive layer and the design layer to partially peel off the resin base layer and the design layer. The decorative laminate from which the resin base layer and design layer had been peeled off was clamped between upper and lower chucks, and the 180-degree peel strength (N / 15 mm) of the decorative laminate was measured using an Autograph AGX-V (manufactured by Shimadzu Corporation) at a temperature of 23°C and a peeling speed of 300 mm / min, in accordance with JIS Z-0237 "Test Method for Adhesive Tapes and Adhesive Sheets". Figure 3 is a schematic diagram showing the state in which the resin base layer and design layer of the decorative laminate are clamped by the upper chuck, and the adhesive layer and heat-resistant film layer are clamped by the lower chuck, illustrating the peel strength measurement method.

[0138] (Detachment test) Each decorative laminate obtained in each example and comparative example was cut to 0.2 cm × 1.5 cm, immersed in 50 g of a 2% aqueous sodium hydroxide (NaOH) solution at 70°C for 72 hours, stirred, then washed with water and dried. The detachability of the adhesive layer from the composite film was observed visually and evaluated according to the following criteria. ○: The entire adhesive layer detached within 72 hours (good). ×: The adhesive layer did not completely detach within 72 hours (defective)

[0139] (Flow during injection molding) PP resin was injected into the heat-resistant film layer side of each decorative laminate obtained in each example and comparative example using an injection molding machine to obtain film insert molded products. The appearance of these film insert molded products was visually observed and evaluated according to the following criteria. ○: No abnormalities in appearance due to deformation of the adhesive layer are observed. △: Appearance abnormalities due to deformation of the adhesive layer are limited to within 10 mm of the gate. ×: The appearance abnormality caused by deformation of the adhesive layer extends more than 10 mm from the gate.

[0140] [Table 1]

[0141] In the examples, excellent results were obtained for all measurement items. In Comparative Example 1, the displacement was high at 20 mm, indicating poor flow during injection molding. In Comparative Example 2, the peel strength was high at 30 N / 15 mm, indicating poor detachability. [Industrial applicability]

[0142] The decorative laminated member of the present invention can be used particularly suitably when performing decoration by insert molding.

Claims

1. A decorative laminate having a heat-resistant film layer, an adhesive layer, a design layer, and a resin substrate layer in this order, In a holding strength test of the decorative laminated member at 80°C, the displacement after 24 hours when a load of 1 kg was applied was 10 mm or less. The peel strength of the decorative laminated member is 20 N / 15 mm or less. When the decorative laminated member is immersed in the release liquid, the adhesive layer exhibits detachability. Laminated material for decorative purposes.

2. The decorative laminated member according to claim 1, further comprising a clear coating layer following a resin substrate layer.

3. The decorative laminate member according to claim 1 or 2, wherein the heat-resistant film layer has a thickness of 200 to 500 μm.

4. The decorative laminate member according to claim 1 or 2, wherein the heat-resistant film layer comprises at least one of polypropylene resin, acrylonitrile-butadiene-styrene (ABS) resin, polycarbonate (PC) resin, polymethyl methacrylate (PMMA) resin, and PC-ABS resin.

5. The aforementioned resin substrate layer consists of at least one of polymethyl methacrylate (PMMA), polycarbonate (PC), and PMMA / PC. A decorative laminate member according to claim 1 or 2, having a thickness of 50 to 300 μm.

6. The aforementioned design layer contains a binder component which is an acrylic resin, and a pigment component which is at least one of a luminous pigment and a coloring pigment. The decorative laminated member according to claim 1 or 2, wherein the pigment component is contained in 0.5 to 60 parts by mass in solid content within 100 parts by mass of the total solid content of the binder component and the pigment component.

7. The decorative laminated member according to claim 2, wherein the clear coating layer is formed by a radiation-curable clear coating layer forming composition or a thermosetting urethane resin composition.

8. A decorative molded product in which a decorative laminated member according to claim 1 or 2 is pressure-bonded and integrated onto the surface of a resin molded body.

9. The decorative molded article according to claim 8, wherein the resin molded article uses the same resin as the heat-resistant film layer.

10. A method for recycling a decorated molded product, comprising immersing the decorated molded product according to claim 8 or 9 in a desorption liquid to recover the heat-resistant film layer and the molded body.

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